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US3830754A - Catalyst composition - Google Patents

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US3830754A
US3830754A US00245934A US24593472A US3830754A US 3830754 A US3830754 A US 3830754A US 00245934 A US00245934 A US 00245934A US 24593472 A US24593472 A US 24593472A US 3830754 A US3830754 A US 3830754A
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catalyst
antimony
tin
vanadium
suspension
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US00245934A
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W Ball
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BP Chemicals Ltd
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BP Chemicals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein

Definitions

  • the present invention relates to a catalytic composition particularly for use in the production of unsaturated aliphatic aldehydes and acids.
  • the components of the catalyst may be mixed in any order, and the catalyst may be prepared in various ways.
  • the antimony and vanadium together with the tin may be co-precipitated from a mixed aqueous so lution of their soluble salts, for example the chlorides.
  • the precipitation may be carried out by the addition of ammonia.
  • the precipitate is then thoroughly washed with water to remove soluble salts, for example, ammonium chloride.
  • an antimony/vanadium oxide composition may be prepared and the tin subsequently incorporated.
  • the antimony/vanadium oxide composition may be prepared by co-precipitation as before or by intimately mixing one or more oxides of antimony such as trioxide, tetroxide, pentoxide or a hydroated oxide with one or more oxidesof vanadium. Mixtures of the oxides or hydrated oxides, for example, those formed by the action of aqueous nitric acid on antimony and vanadium metals or on mixtures of metals may also be used. In this case the mixed oxide composition contains residual nitrate ion and this may be removed by washing either with hot water or with a dilute solution of ammonia or an organic base.
  • the tin may then be added to the mixture, for example, as an insoluble neutral compound which is convertible to oxide on heating.
  • insoluble neutral compounds are the hydroxide, carbonate and hydrated oxide.
  • the tin may be added to the antimony/vanadium composition in the form of a soluble salt or salts such as a nitrate, formate, acetate, chloride or sulphate, the oxides then being precipitated by the addition of a base such as ammonia.
  • a preferred method of preparing the catalyst comprises mixing finely divided vanadium pentoxide with a slurry or suspension in water of the other oxides or hydrated oxides.
  • the present invention is a'catalyst, suitable for catalysing the vapour phase oxidation of propylene, with molecular oxygen to produce acrolein together with acrylic acid, which comprises an oxide composition containing antimony, vanadium and tin prepared by adding most ammonium vanadate to a suspension of antimony trioxide in nitric acid, addingpowdered tin to the resultant suspension, thereafter.
  • the proportions of the various components of the oxide composition catalyst may vary within moderately wide limits.
  • the composition contains an excess of antimony over any other single component and preferably an atomic ratio of antimony to vanadium within the range 1.5:.1 to 4: 1; or more especially between 2.0:1 and 3.0:1. It is preferred to have an atomic ratio of vanadium to tin the range 1:0.25 to 1:2.
  • the pH of the suspensions of solid on resuspended solid is preferably adjusted to between 7 and 9 and especially in the range 7.2 to 8.
  • the pH may be adjusted an any convenient manner for example by addition of ammonia or other water soluble nitrogenous base e.g. aliphatic amines, eflhanolamine, ethylamiine, triethylamine, ethylene diamine aromatic or heterocyclic amines such as aniline, pyridine, cycloaliphatic amines such as piperidine and compounds such as hydrazine.
  • the recovered solid is heated preferably first prior to pelleting in an inert atmosphere to a temperature in the range 200 to 500 C.
  • the inert atmosphere may be any which does not react with the composition. Suitable examples of gases which may constitute an inert atmosphere are nitrogen or argon.
  • the solid thus heated may thereafter be pelleted and the pellets subjected for a further heat treatment at a temperature within the range 550 to 1000" C. preferably 700 to 900 C. and more especially between 750 and 850 C., in a molecular oxygen containing gas e.g. air.
  • the time of heating is not critical and may be, for example, from about 4 hours to about 40 hours. The rate of heating may be varied within wide limits. Thus for example the catalyst may be heated to C.
  • the supply of molecular oxygen containing gas e.g. air at this time is preferably adjusted to leave a concentration of oxygen in excess of 5% in the gases leaving the heating furnace. It has been found that the prior heat treatment of the oxide composition is essential in order for it to be of value as a catalyst in the commercial scale process.
  • the oxide composition catalysts may if desired, be deposited upon supports such as alumina, pumice, silica or titania.
  • the reaction of propylene with molecular oxygen over the oxide composition catalysts may be carried out in any suitable manner, for instance, as a fixed bed process in which the catalyst is used in the form of granules or pellets, or as a fluidised bed process, or as a moving bed process.
  • the proportion of propylene in the feed to the reaction may vary within fairly wide limits, for example between 3 1 and 20% by volume of the feed,and suitably between 2 and 10% by volume, v
  • concentration of oxygen in the feed may also vary within moderately wide limits, for example between 1 and 20% by volume and preferably between 2 and 15% by volume.
  • the oxygen may be diluted with inert gases, and may be, for example, supplied as air.
  • reaction it is preferred to carry out the reaction in the presence of a gas which is substantially inert under the'conditions of reaction, for example, nitrogen, propane, butane, .isobutane, carbon dioxide and/or steam. It is preferred to use steam or nitrogen or mixtures thereof.
  • concentration of the steam may vary within limits, for example, between 10 and 60% by volume of the feed.
  • the reaction is carried out at an elevated temperature, for instance between 250 C. and 550 C. and preferably between 300 and 500 C.
  • the reaction may also be carried out under pressure for example pressures of from 0.5 to 5 atmospheres absolute.
  • the contact time may be, for example, in the range /2 to 30 seconds and preferably between 1 and 5 seconds.
  • the acrolein acrylic acid may be recovered from the reaction product by any conventional method, for example, by condensation or extraction with water and distillation.
  • Moist ammonium metavanadate paste (vanadium content 41.4% weight; 2755 parts by weight) was added over 25 minutes to a mechanical stirred suspension of antimony trioxide (4664 parts by weight) in concentrated 70% nitric acid (13,400 parts by weight) and distilled water (24,000 parts by weight) at 95 C., powdered tin (1898 parts by weight) was added over 40 minutes, stirring continued for a further 15 minutes, then the mixture cooled to 30 C. and filtered. The filter-cake was suspended in distilled water (24,000 parts by weight and the pH raised by the addition of aqueous ammonia solution (see table 'below).
  • the mixture was cooled to 30 C., filtered and the filter-cake washed once by resuspension for 15 minutes in distilled Water.
  • the final filter-cake was dried 120 C. broken down to pass 18 mesh (B.S.S.) and heat-treated at 380 C. for 3 hours in an atmosphere of nitrogen.
  • the dry product was mixed with graphite (1% by weight), pelleted and the pellets heated to 850 C. in a stream of air, the temperature being raised from 200 C. at the rate of 20 C. per hour, then maintained at 850 C. for 16 hours.
  • the reactor inlet pressure was 40 p.s.i.g.
  • the results obtained are given in the following table:
  • a actalyst suitable for catalysing'the vapor phase" oxidation of propylene with molecular oxygen to produce" acrolein together with acrylic acid, which comprises an oxide composition containing antimony, vanadium and tin prepared by adding ammonium vanadate'to a-suspension of antimony trioxide in nitric acid,'adding powdered tin to the resultant suspension, adjusting the pH of the suspension to 7 or above, recovering suspended solid, and finally heating the recovered solid in a molecular oxygen containing gas at a temperature in the range 5 50. to 1,000 c.
  • a catalyst as defined in claim 1 wherein, prior to adjustment of the pH of the suspension, solids are recovered from the suspension and resuspended in water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

CATALYST COMPOSITIONS CONTAINING ANTIMONY, VANADIUM AND TIN ARE PREPARED BY ADDITION OF MOIST AMMONIUM VANADATE TO A SUSPENSION OF ANTIMONY TRIOXIDE IN NITRIC ACID FOLLOWED BY ADDITION OF POWDERED TIN AND RECOVERY AND HEATING OF SOLID.

Description

Claims priority, application Great Britain,
us. Cl. 252-456 United States Patent Oflice 3,830,754 Patented Aug. 20, 1974 3,830,754 CATALYST COMPOSITION William John Ball, Capel, England, assignor to RP Chemicals International Limited, London, England No Drawing. Filed Apr. 20, 1972, Ser. No. 245,934
10,674/ 71 Int. Cl. B01j 11/06, 11/32 9 Claims acid followed by addition of powdered tin and recovery and heating of solid.
The present invention relates to a catalytic composition particularly for use in the production of unsaturated aliphatic aldehydes and acids.
British Patent Specification No. 1,034,914 (Distillers) describes and claims a process for the production of may be employed is an oxide composition containing antimony, vanadium and tin.
The components of the catalyst may be mixed in any order, and the catalyst may be prepared in various ways. For instance, the antimony and vanadium together with the tin may be co-precipitated from a mixed aqueous so lution of their soluble salts, for example the chlorides. In this case the precipitation may be carried out by the addition of ammonia. The precipitate is then thoroughly washed with water to remove soluble salts, for example, ammonium chloride.
Alternatively an antimony/vanadium oxide composition may be prepared and the tin subsequently incorporated. The antimony/vanadium oxide composition may be prepared by co-precipitation as before or by intimately mixing one or more oxides of antimony such as trioxide, tetroxide, pentoxide or a hydroated oxide with one or more oxidesof vanadium. Mixtures of the oxides or hydrated oxides, for example, those formed by the action of aqueous nitric acid on antimony and vanadium metals or on mixtures of metals may also be used. In this case the mixed oxide composition contains residual nitrate ion and this may be removed by washing either with hot water or with a dilute solution of ammonia or an organic base. The tin may then be added to the mixture, for example, as an insoluble neutral compound which is convertible to oxide on heating. Examples of such insoluble neutral compounds are the hydroxide, carbonate and hydrated oxide. Alternatively the tin may be added to the antimony/vanadium composition in the form of a soluble salt or salts such as a nitrate, formate, acetate, chloride or sulphate, the oxides then being precipitated by the addition of a base such as ammonia. A preferred method of preparing the catalyst comprises mixing finely divided vanadium pentoxide with a slurry or suspension in water of the other oxides or hydrated oxides.
It has now been found possible to increase the activity and selectivity of an oxide composition containing antimony, vanadium and tin as catalyst for the oxidation of Apr. 22, 1911, v
acrolein (or propylene) to produce acrylic acid by adopting a particular method of preparation. 7
Accordingly the present invention is a'catalyst, suitable for catalysing the vapour phase oxidation of propylene, with molecular oxygen to produce acrolein together with acrylic acid, which comprises an oxide composition containing antimony, vanadium and tin prepared by adding most ammonium vanadate to a suspension of antimony trioxide in nitric acid, addingpowdered tin to the resultant suspension, thereafter.
(a) adjusting the pH of the suspension to 7 or above and recovering suspended solid, or
(b) recovering solid from the suspension, resuspending in water, adjusting the pH of the suspension to 7 or above and recovering suspended solid,
and finally heating the recovered solid in a molecular oxygen containing gas at a temperature in the range 550- 1000 C.
The proportions of the various components of the oxide composition catalyst may vary within moderately wide limits. Suitably the composition contains an excess of antimony over any other single component and preferably an atomic ratio of antimony to vanadium within the range 1.5:.1 to 4: 1; or more especially between 2.0:1 and 3.0:1. It is preferred to have an atomic ratio of vanadium to tin the range 1:0.25 to 1:2.
The pH of the suspensions of solid on resuspended solid is preferably adjusted to between 7 and 9 and especially in the range 7.2 to 8. The pH may be adjusted an any convenient manner for example by addition of ammonia or other water soluble nitrogenous base e.g. aliphatic amines, eflhanolamine, ethylamiine, triethylamine, ethylene diamine aromatic or heterocyclic amines such as aniline, pyridine, cycloaliphatic amines such as piperidine and compounds such as hydrazine.
The recovered solid is heated preferably first prior to pelleting in an inert atmosphere to a temperature in the range 200 to 500 C. The inert atmosphere may be any which does not react with the composition. Suitable examples of gases which may constitute an inert atmosphere are nitrogen or argon. The solid thus heated may thereafter be pelleted and the pellets subjected for a further heat treatment at a temperature within the range 550 to 1000" C. preferably 700 to 900 C. and more especially between 750 and 850 C., in a molecular oxygen containing gas e.g. air. The time of heating is not critical and may be, for example, from about 4 hours to about 40 hours. The rate of heating may be varied within wide limits. Thus for example the catalyst may be heated to C. and then at an average rate of 50/ hour preferably between 10 and 25/hour until the desired upper limit of temperature is reached. The supply of molecular oxygen containing gas e.g. air at this time is preferably adjusted to leave a concentration of oxygen in excess of 5% in the gases leaving the heating furnace. It has been found that the prior heat treatment of the oxide composition is essential in order for it to be of value as a catalyst in the commercial scale process.
The oxide composition catalysts may if desired, be deposited upon supports such as alumina, pumice, silica or titania.
The reaction of propylene with molecular oxygen over the oxide composition catalysts may be carried out in any suitable manner, for instance, as a fixed bed process in which the catalyst is used in the form of granules or pellets, or as a fluidised bed process, or as a moving bed process.
The proportion of propylene in the feed to the reaction may vary within fairly wide limits, for example between 3 1 and 20% by volume of the feed,and suitably between 2 and 10% by volume, v
'T he concentration of oxygen in the feed may also vary within moderately wide limits, for example between 1 and 20% by volume and preferably between 2 and 15% by volume. The oxygen may be diluted with inert gases, and may be, for example, supplied as air.
It is preferred to carry out the reaction in the presence of a gas which is substantially inert under the'conditions of reaction, for example, nitrogen, propane, butane, .isobutane, carbon dioxide and/or steam. It is preferred to use steam or nitrogen or mixtures thereof. The concentration of the steam may vary within limits, for example, between 10 and 60% by volume of the feed.
The reaction is carried out at an elevated temperature, for instance between 250 C. and 550 C. and preferably between 300 and 500 C. The reaction may also be carried out under pressure for example pressures of from 0.5 to 5 atmospheres absolute.
The contact time may be, for example, in the range /2 to 30 seconds and preferably between 1 and 5 seconds.
The acrolein acrylic acid may be recovered from the reaction product by any conventional method, for example, by condensation or extraction with water and distillation.
The process of the invention is further illustrated by the following example:
EXAMPLE A series of catalysts were prepared as described below.
Moist ammonium metavanadate paste (vanadium content 41.4% weight; 2755 parts by weight) was added over 25 minutes to a mechanical stirred suspension of antimony trioxide (4664 parts by weight) in concentrated 70% nitric acid (13,400 parts by weight) and distilled water (24,000 parts by weight) at 95 C., powdered tin (1898 parts by weight) was added over 40 minutes, stirring continued for a further 15 minutes, then the mixture cooled to 30 C. and filtered. The filter-cake was suspended in distilled water (24,000 parts by weight and the pH raised by the addition of aqueous ammonia solution (see table 'below). The mixture was cooled to 30 C., filtered and the filter-cake washed once by resuspension for 15 minutes in distilled Water. The final filter-cake was dried 120 C. broken down to pass 18 mesh (B.S.S.) and heat-treated at 380 C. for 3 hours in an atmosphere of nitrogen. The dry product was mixed with graphite (1% by weight), pelleted and the pellets heated to 850 C. in a stream of air, the temperature being raised from 200 C. at the rate of 20 C. per hour, then maintained at 850 C. for 16 hours.
The catalysts were tested by passing a gaseous mixture of by volume 7% propylene, 63% air and 30% steam over the catalyst in a reactor at ca. 340=370 C. and 3 seconds contact time (calculated N.T.-P.). The reactor inlet pressure was 40 p.s.i.g. The results obtained are given in the following table:
Yield ofaerylie; acid based on pH of suspension propylene fed propylene fed propylene {ed The above data clearly demonstrates 'the improved combined yield of acrolein/ acrylic acid obtainable byns6 of the catalyst of the present invention.
1. A actalyst, suitable for catalysing'the vapor phase" oxidation of propylene with molecular oxygen to produce" acrolein together with acrylic acid, which comprises an oxide composition containing antimony, vanadium and tin prepared by adding ammonium vanadate'to a-suspension of antimony trioxide in nitric acid,'adding powdered tin to the resultant suspension, adjusting the pH of the suspension to 7 or above, recovering suspended solid, and finally heating the recovered solid in a molecular oxygen containing gas at a temperature in the range 5 50. to 1,000 c.
2. A catalyst as claimed in Claim 1 wherein the oxide composition contains an excess of antimony over any" other single component.
3. A catalyst as claimed in Claim 1 wherein the oxide composition contains antimony and vanadium in atomic ratio within the range of 1.5:1 to 4: 1. v v H 4. .A catalyst as claimed in Claim 1 containing vana dium and tin in atomic ratio 1:0.25 to 1:2. I
5. A catalyst as claimed in Claim 1 wherein the pH of the suspension is adjusted to between 7 and 9.
6. A catalyst as claimed in Claim 1 wherein the fecovered solid is heated in an inert atmosphere to a temperature in the range 200 to 500 C., the heated solid thereafter is pelleted and the pellets subjected to a further heating at a temperature within the range 550 to 1,000 C., in a molecular oxygen container gas. p
7. A catalyst as claimed in Claim 1 depositedupon a support material. p
8. A catalyst as claimed in Claim 7 wherein the support material is selected from alumina, pumice, silica and titania.
9. A catalyst as defined in claim 1 wherein, prior to adjustment of the pH of the suspension, solids are recovered from the suspension and resuspended in water.
References Cited UNITED STATES PATENTS 3,554,931 '1/1971 Brown .....a 252-461 X 3,269,957 8/1966 Bethell 252461 3,579,574 5/1971 Van der Meer 2 -530 CA RL' F. DEES, Primary Examiner '2 US. Cl. X.R.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 8 ,7 Dated August 20, 1974 Inventor-( It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Col. 1, line 31, correct the spelling of "range" Col. 2, line 8, "most" should read "moist" Col. 2, line 32, "an" should read "in" Col. 4, line 13, claim 1, correct the spelling of "catalyst".
Signed and sealed this 2th day of November 1974.
'(SEAL) Attest:
McCOY M. GIBSON JR. 0. MARSHALL DANN Attesting Officer Commissioner of Patents FORM PO-IOSO (10-69)
US00245934A 1971-04-22 1972-04-20 Catalyst composition Expired - Lifetime US3830754A (en)

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CA (1) CA976947A (en)
DE (1) DE2219297A1 (en)
FR (1) FR2133995B1 (en)
GB (1) GB1324573A (en)
IT (1) IT983231B (en)
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ZA (1) ZA722578B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11219859B2 (en) * 2016-07-26 2022-01-11 Basf Corporation Supported catalyst, monolithic selective catalytic reduction (SCR) catalyst, preparation method therefor, and method for nitrogen oxides removal

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11219859B2 (en) * 2016-07-26 2022-01-11 Basf Corporation Supported catalyst, monolithic selective catalytic reduction (SCR) catalyst, preparation method therefor, and method for nitrogen oxides removal

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GB1324573A (en) 1973-07-25
FR2133995A1 (en) 1972-12-01
ZA722578B (en) 1973-11-28
BE782524A (en) 1972-10-23
IT983231B (en) 1974-10-31
NL7205322A (en) 1972-10-24
AU4144272A (en) 1973-10-25
DE2219297A1 (en) 1972-11-02
CA976947A (en) 1975-10-28
FR2133995B1 (en) 1975-10-24

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